TWI807837B - Material with slippery protective coating and manufacturing method of slippery protective coating - Google Patents

Abstract

A manufacturing method of a slippery protective coating is provided according to the present disclosure. The manufacturing method includes steps as follows. A material with low surface energy and a surfactant are provided, a micro-particle dispersion preparing step is performed, a micro-particle dispersion coating step is performed and a lubricant coating step is performed. In the micro-particle dispersion preparing step, the material with low surface energy and the surfactant are evenly mixed to form a micro-particle dispersion. In the micro-particle dispersion coating step, the micro-particle dispersion is coated on a substrate, and the substrate is heated to form an adhesion layer and a porous layer on the substrate. In the lubricant coating step, a lubricant is coated on the porous layer, so as to form a slippery protective coating. Therefore, the slippery protective coating fabricated by the manufacturing method of the present disclosure has great antifouling ability, and is safe to the environment and creatures.

Description

Material with smooth protective coating and method for preparing smooth protective coating

The present invention relates to a material with a smooth protective coating and a preparation method for a smooth protective coating, in particular to a material with a smooth protective coating and a preparation method for a corrosion-resistant, anti-adhesion, self-repairing, antifreeze and self-cleaning material with a smooth protective coating.

The known anti-fouling methods can be divided into three categories: the first type is manual mechanical scraping after dirt bio-adhesion, the second type is coating organic tin or cuprous oxide and other paints, and the third type is non-toxic anti-bio-fouling strategies. The above-mentioned anti-fouling methods all have their disadvantages. For example, the first type of method consumes a lot of money, time and manpower, is inefficient and cannot prevent dirt bio-adhesion; the second type of method is to gradually release toxic substances as the paint degrades, which is a non-selective biocidal method, which is easy to harm other organisms; the third type of method is to achieve anti-fouling effects by manufacturing hydrophilic, hydrophobic or bionic surface structures.

In addition, anti-corrosion and anti-biofouling technologies for underwater appliances are still to be studied. At present, the commercially available paints are mainly anti-corrosion, and the surface of the material painted with anti-corrosion paint tends to become rough, which is conducive to the adhesion of biological fouling, and the chemical substances or enzymes produced by the biological fouling will further erode the paint, resulting in a decrease in the corrosion resistance of the paint and the need for regular repainting, followed by high maintenance costs. On the other hand, most anti-corrosion paints are not transparent, and light cannot penetrate the paint, so the application of anti-corrosion paints will be limited.

In view of this, the development of a protective coating that can exert an anti-fouling effect for a long time and is friendly to the environment and organisms is still the goal of the relevant industry.

To achieve the above goals, the present invention provides a smooth protective coating, the material combination of which can achieve long-term anti-fouling and low toxicity effects.

One aspect of the present invention provides a method for preparing a lubricious protective coating formed on a substrate to be protected. The preparation method comprises the following steps: providing a low surface energy material, providing a surfactant, performing a microparticle dispersion preparation step, performing a microparticle dispersion coating step and performing a lubricant coating step. In the step of preparing the particle dispersion, the low surface energy material and the surfactant are uniformly mixed to form a particle dispersion, and the particle dispersion contains a plurality of particles formed by the low surface energy material. In the microparticle dispersion coating step, the microparticle dispersion is coated on the substrate, and the substrate coated with the microparticle dispersion is heat-treated to form an adhesive layer and a hole layer on the substrate. The hole layer is formed by particles, and the adhesive layer is formed by a surfactant and is located between the hole layer and the substrate. In the lubricant coating step, a lubricant is coated on the hole layer, and the lubricant penetrates into the hole structure of the hole layer to form a smooth protective coating on the base material. Wherein, the smooth protective coating includes a hole layer, an adhesive layer and a lubricant.

Accordingly, the preparation method of the smooth protective coating of the present invention is easy to operate, which is conducive to mass production and practical use in the industry, and the low surface energy materials, surfactants and lubricants selected in the preparation method of the present invention have low toxicity and low pollution, and can ensure that they will not cause harm to the environment and organisms on the premise of having a good antifouling effect.

According to the preparation method of the aforementioned smooth protective coating, the low surface energy material can be polytetrafluoroethylene or polydimethylsiloxane.

According to the aforementioned method for preparing a smooth protective coating, when the low surface energy material is polytetrafluoroethylene, the diameter of each particle in the particle dispersion can be 100 nm to 300 nm.

According to the preparation method of the aforementioned smooth protective coating, wherein when the low surface energy material is polydimethylsiloxane, the diameter of each particle in the particle dispersion can be 10 μm to 40 μm.

According to the preparation method of the aforementioned smooth protective coating, wherein the surfactant can be polyethylene glycol trimethyl nonyl ether.

According to the preparation method of the aforementioned smooth protective coating, the volume percentage concentration of the particles in the particle dispersion can be 10% to 60%.

According to the preparation method of the aforementioned lubricating protective coating, the lubricant can be ionic liquid, silicon oil or fluorine lubricating oil.

According to the preparation method of the aforementioned smooth protective coating, wherein in the step of coating the particle dispersion, the substrate coated with the particle dispersion can be heat-treated at a temperature of 100°C to 150°C for 5 minutes to 15 minutes.

According to the preparation method of the aforementioned smooth protective coating, the thickness of the smooth protective coating may be 300 nm to 500 nm.

Another aspect of the present invention provides a material with a smooth protective coating, which includes a substrate and a smooth protective coating. The substrate has a surface, and a smooth protective coating is formed on the surface of the substrate, and the smooth protective coating is prepared by the aforementioned preparation method of the smooth protective coating.

Various embodiments of the invention are discussed in more detail below. However, this embodiment may be an application of various inventive concepts, and may be embodied in various specific ranges. The specific embodiments are for illustrative purposes only and do not limit the scope of the disclosure.

Please refer to FIG. 1 and FIG. 2. FIG. 1 is a flow chart of the steps of the method 100 for preparing a smooth protective coating of the present invention, and FIG. 2 is a schematic cross-sectional view of a material 200 with a smooth protective coating of the present invention. The preparation method 100 of the smooth protective coating is to form a smooth protective coating 220 on a substrate 210 to be protected, and the preparation method 100 of the smooth protective coating includes step 110 , step 120 , step 130 , step 140 and step 150 .

Step 110 is to provide a low surface energy material, wherein the low surface energy material can be polytetrafluoroethylene (PTFE) or polydimethylsiloxane (PDMS). Step 120 is to provide a surfactant, wherein the surfactant may be polyethylene glycol trimethylnonyl ether (2-[(2,6,8-Trimethyl-4-nonanyl) oxy]ethanol).

Step 130 is the step of preparing a particle dispersion. In this step, the low surface energy material and the surfactant are uniformly mixed to form a particle dispersion, and the particle dispersion contains a plurality of particles formed by the low surface energy material, and the volume percentage concentration of the particles in the particle dispersion can be 10% to 60%. Please also refer to Figure 3A. Figure 3A is a transmission electron microscope image of the particle dispersion. It can be seen from Figure 3A that the particle dispersion contains particles (dark areas) formed by low surface energy materials, and the surfactant (pointed by the white arrow) is evenly dispersed among the particles, which can avoid the uneven distribution of particles due to aggregation.

In addition, when the low surface energy material is polytetrafluoroethylene, the diameter of each particle in the particle dispersion can be 100 nm to 300 nm; when the low surface energy material is polydimethylsiloxane, the diameter of each particle in the particle dispersion can be 10 μm to 40 μm.

Step 140 is a particle dispersion coating step. In this step, the particle dispersion is coated on the substrate 210, and the substrate 210 coated with the particle dispersion is heat-treated to form an adhesive layer 222 and a hole layer 221 on the substrate 210. The hole layer 221 is formed by particles, and the adhesive layer 222 is formed by a surfactant and is located between the hole layer 221 and the substrate 210. Wherein, the substrate 210 coated with the particle dispersion can be heat-treated at a temperature of 100° C. to 150° C. for 5 minutes to 15 minutes.

Please refer to Figure 3B and Figure 3C. Figure 3B is a scanning electron microscope image of the substrate coated with the particle dispersion before heat treatment in the particle dispersion coating step, and Figure 3C is a scanning electron microscope image of the substrate coated with the particle dispersion in the particle dispersion coating step after heat treatment. It can be seen from the cross-sectional view on the upper right of Figure 3B that before the heat treatment of the substrate coated with the particle dispersion, the particles on the surface of the substrate are coated by the surfactant. After the heat treatment, the surfactant flows down and stays between the particles and the substrate, forming a structure as shown in the cross-sectional view on the upper right of Figure 3C. At this time, the water contact angle (WCA) on the surface of the substrate is close to 130 degrees, which means that the surface of the substrate is quite hydrophobic at this time.

Please refer to Figure 1 and Figure 2 again. Step 150 is a lubricant coating step. In this step, a lubricant 223 is applied to the hole layer 221, and the lubricant 223 penetrates into the hole structure of the hole layer 221 to form a smooth protective coating 220 on the substrate 210. Wherein, the smooth protective coating 220 includes a hole layer 221, an adhesive layer 222, and a lubricant 223. The thickness of the smooth protective coating 220 may be 300 nm to 500 nm, and the lubricant 223 may be ionic liquid, silicon oil or fluorine lubricating oil.

Please refer to FIG. 2 and FIG. 3D. FIG. 3D is a scanning electron microscope image of the material 200 with a smooth protective coating of the present invention. The material 200 with a smooth protective coating includes a substrate 210 and a smooth protective coating 220. The smooth protective coating 220 is formed on the surface of the substrate 210, and the smooth protective coating 220 is prepared by the aforementioned method 100 for preparing a smooth protective coating, so details are not repeated here. It can be seen from FIG. 3D that the surface of the smooth protective coating 220 is flat, which means that the lubricant 223 has penetrated into the hole layer 221 and filled the hole structure of the hole layer 221 to form a smooth surface to provide a good antifouling effect.

In the following, the material with a smooth protective coating of the present invention will be tested to understand its optical properties, mechanical strength, chemical resistance and anti-biological adhesion properties.

＜Abrasion resistance test＞

This experiment is to test the wear resistance of the first embodiment and the first comparative example. Wherein, the substrate of the first embodiment is a metal substrate, and the smooth protective coating is prepared by the preparation method of the smooth protective coating of the present invention. The low surface energy material used is polytetrafluoroethylene, and the surfactant is polyethylene glycol trimethylnonyl ether; the preparation steps of the smooth protective coating in the first comparative example are roughly the same as those of the first embodiment, and the difference is that the first comparative example does not contain a surfactant.

Please refer to FIG. 4A and FIG. 4B . FIG. 4A and FIG. 4B are the coating adhesion test results of the first embodiment and the first comparative example respectively. In detail, Figure 4A and Figure 4B are microscopic images of the surface of the first embodiment and the first comparative example after being washed by a strong water column and ground with 300-grit sandpaper. It can be seen from Figure 4A and Figure 4B that the coating of the first comparative example has peeled off obviously after the test, while the smooth protective coating of the first embodiment is almost intact and maintains good hydrophobicity. It can be seen that the material with a smooth protective coating of the present invention has excellent wear resistance, can prolong the service life and provide long-term protection effect.

＜Light transmittance test＞

In this experiment, light transmittance tests are carried out for the second to fourth embodiments, the second comparative example, and the third comparative example. Wherein, the second comparative example is an unprocessed glass substrate, the smooth protective coatings of the second to fourth examples are prepared by the preparation method of the smooth protective coating of the present invention, and the preparation steps of the smooth protective coatings of the third comparative example are roughly the same as those of the second to fourth examples, the difference being that the materials used are different. The materials used in the second embodiment to the fourth embodiment, the second comparative example and the third comparative example are listed in Table 1 below, and will not be repeated here. Table I Substrate Low Surface Energy Materials Surfactant lubricant 2nd embodiment Glass PTFE Polyethylene glycol trimethyl nonyl ether Fluorine lubricating oil 3rd embodiment ionic liquid 4th embodiment silicone oil The second comparative example none none none 3rd comparative example PTFE Polyethylene glycol trimethyl nonyl ether none

Please refer to FIG. 5A and FIG. 5B. FIG. 5A is a comparative graph of the transmittance of the second comparative example, the third comparative example and the second embodiment, and FIG. 5B is a comparative graph of the transmittance of the second embodiment, the third embodiment and the fourth embodiment. It can be seen from Figure 5A that the transmittance of the second comparative example in the visible light region (wavelength 380 nm to 760 nm) is only about 90%, and the transmittance of the third comparative example is better than that of the second comparative example, but the transmittance is obviously insufficient at short wavelengths (wavelength less than 500 nm). On the other hand, it can be seen from Figure 5A and Figure 5B that the transmittance in the visible light region of the second embodiment to the fourth embodiment can reach 92%, which means that the smooth protective coating prepared by the preparation method of the smooth protective coating of the present invention is not easy to block the passage of light, so the material with a smooth protective coating of the present invention is suitable for precision instruments such as medical testing and optical analysis.

＜Acid corrosion resistance test＞

In this experiment, the acid corrosion resistance test is carried out for the fifth embodiment, the fourth comparative example and the fifth comparative example. Wherein, the substrate of the fifth embodiment is a copper substrate, and its smooth protective coating is prepared by the preparation method of the smooth protective coating of the present invention. The low surface energy material used is polytetrafluoroethylene, the surfactant is polyethylene glycol trimethylnonyl ether, and the lubricant is fluorine lubricating oil; the fourth comparative example is an unprocessed copper substrate; the fifth comparative example is a copper substrate coated with acrylic resin (Acrylic resin). Specifically, in this experiment, the fifth embodiment, the fourth comparative example, and the fifth comparative example were soaked in 0.1 M hydrochloric acid aqueous solution, and after standing for 7 days, they were taken out and their rust conditions were observed.

Please refer to Fig. 6A to Fig. 6C. Fig. 6A, Fig. 6B and Fig. 6C are the acid corrosion test results of Comparative Example 4, Comparative Example 5 and Example 5 respectively. From Figures 6A to 6C, it can be seen that the copper substrate of Comparative Example 4 has obvious corrosion (reddish brown), and Comparative Example 5 also has slight corrosion (orange), while the copper substrate of Example 5 is only acid-etched around, and the original metallic luster of the copper substrate is still maintained in the center.

＜Alkali Corrosion Resistance Test＞

In this experiment, the alkali corrosion resistance test is carried out for the sixth embodiment, the sixth comparative example and the seventh comparative example. Wherein, the substrate of the sixth embodiment is an aluminum substrate, and its smooth protective coating is prepared by the preparation method of the smooth protective coating of the present invention. The low surface energy material used is polytetrafluoroethylene, the surfactant is polyethylene glycol trimethylnonyl ether, and the lubricant is fluorine lubricating oil; the sixth comparative example is an unprocessed aluminum substrate; the seventh comparative example is an aluminum substrate coated with acrylic resin. In detail, in this experiment, the sixth embodiment, the sixth comparative example and the seventh comparative example were soaked in 0.1 M sodium hydroxide aqueous solution, and after standing for 7 days, they were taken out and their rust conditions were observed.

Please refer to Fig. 7A to Fig. 7C. Fig. 7A, Fig. 7B and Fig. 7C are the alkali corrosion test results of Comparative Example 6, Comparative Example 7 and Example 6 respectively. From Figures 7A to 7C, it can be seen that the aluminum substrate of Comparative Example 6 has been severely corroded and has become damaged. The alkali corrosion resistance of the smooth protective coating of Example 6 is equivalent to that of the acrylic resin of Comparative Example 7. There is no significant difference between the aluminum substrates of the two before and after soaking in alkaline solution. This shows that the smooth protective coating prepared by the method for preparing a smooth protective coating according to the present invention can effectively protect the substrate in an alkaline environment and prevent the substrate from being corroded.

＜Anti-biological adhesion test＞

In this experiment, the anti-biological adhesion test was carried out for the fifth embodiment to the tenth embodiment and the fourth comparative example to the ninth comparative example. Among them, the preparation methods and materials of the fifth embodiment, the sixth embodiment, and the fourth to seventh comparative examples are as described in the preceding paragraphs, the smooth protective coatings of the seventh to tenth embodiments are prepared by the preparation method of the smooth protective coating of the present invention, the preparation steps of the eighth and ninth comparative examples are roughly the same as those of the seventh to tenth embodiments, and the difference lies in the materials used. The materials used in the fifth embodiment to the tenth embodiment and the fourth comparative example to the ninth comparative example are listed in Table 2 below, and will not be repeated here. Table II Substrate Low Surface Energy Materials Surfactant lubricant fifth embodiment copper PTFE Polyethylene glycol trimethyl nonyl ether Fluorine lubricating oil sixth embodiment aluminum Fluorine lubricating oil Seventh embodiment copper ionic liquid Eighth embodiment aluminum ionic liquid 9th embodiment copper silicone oil 10th embodiment aluminum silicone oil 4th comparative example copper none none none 5th comparative example copper Acrylic none none Comparative Example 6 aluminum none none none 7th comparative example aluminum Acrylic none none 8th comparative example copper PTFE Polyethylene glycol trimethyl nonyl ether none Comparative Example 9 aluminum none

Specifically, the above-mentioned examples and comparative examples were cultured together with the algae suspension for 7 days at 28° C. under a weak light environment, and the concentration of the algae suspension was about 10 ⁷ algae cells per milliliter. Please refer to FIG. 8 . FIG. 8 is a comparison chart of the anti-algae adhesion capabilities of the fourth comparative example to the ninth comparative example and the fifth embodiment to the tenth embodiment. It can be known from Figure 8 that the anti-adhesion ability of the seventh embodiment to the tenth embodiment is better than that of the fifth comparative example and the seventh comparative example to the ninth comparative example, and the anti-adhesion ability of the fifth embodiment, the sixth embodiment, the ninth embodiment and the tenth embodiment is significantly better than the fourth comparative example and the sixth comparative example. The effect of biofouling.

＜Self-healing test＞

This experiment is a self-repair test for the eleventh embodiment. In detail, the smooth protective coating of the eleventh embodiment is prepared by the preparation method of the smooth protective coating of the present invention. The low surface energy material used is polytetrafluoroethylene, the surfactant is polyethylene glycol trimethylnonyl ether, and the lubricant is fluorine lubricating oil. In this experiment, after the material with a smooth protective coating in the eleventh embodiment is destroyed, it is placed at room temperature and its surface changes are observed.

Please refer to FIG. 9, which is a self-repair test diagram of the eleventh embodiment. It can be seen from Figure 9 that the material with a smooth protective coating of the eleventh embodiment has obvious scratches (pointed by the arrow) after being destroyed, and after standing for about nine minutes, the scratches on the surface of the material have almost disappeared.

To sum up, the preparation method of the lubricating protective coating of the present invention is easy to operate, which is conducive to mass production and practical use in the industry, and the low surface energy materials, surfactants and lubricants selected in the preparation method of the present invention have low toxicity and low pollution, and can ensure that they will not cause harm to the environment and organisms under the premise of having a good antifouling effect.

Although the present invention has been disclosed as above with the embodiments, it is not intended to limit the present invention. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be as defined by the scope of the appended patent application.

100: Preparation method of smooth protective coating 110,120,130,140,150: steps 200: Material with smooth protective coating 210: Substrate 220: smooth protective coating 221: hole layer 222: Adhesive layer 223: lubricant

In order to make the above and other objects, features, advantages and embodiments of the present invention more clearly understood, the accompanying drawings are described as follows: Fig. 1 is a flow chart of the steps of the preparation method of the smooth protective coating of the present invention; Fig. 2 is a schematic cross-sectional view of a material with a smooth protective coating of the present invention; Figure 3A is a transmission electron microscope image of a particle dispersion; Figure 3B is a scanning electron microscope image of the substrate coated with the particle dispersion before heat treatment in the particle dispersion coating step; Figure 3C is a scanning electron microscope image of the substrate coated with the particle dispersion after heat treatment in the particle dispersion coating step; Figure 3D is a scanning electron microscope image of a material with a smooth protective coating of the present invention; Fig. 4A and Fig. 4B are respectively the coating adhesion test result diagrams of the first embodiment and the first comparative example; Figure 5A is a comparison chart of the transmittance of the second comparative example, the third comparative example and the second embodiment; Fig. 5B is a comparative diagram of the penetration rate of the second embodiment, the third embodiment and the fourth embodiment; Fig. 6A, Fig. 6B and Fig. 6C are the acid corrosion test results of the fourth comparative example, the fifth comparative example and the fifth embodiment respectively; Fig. 7A, Fig. 7B and Fig. 7C are the alkali corrosion test result diagrams of the 6th comparative example, the 7th comparative example and the 6th embodiment respectively; Fig. 8 is a comparison chart of the anti-algae adhesion ability of the 4th comparative example to the 9th comparative example and the 5th embodiment to the 10th embodiment; and Fig. 9 is a self-repair test diagram of the eleventh embodiment.

100: Preparation method of smooth protective coating

110,120,130,140,150: steps

Claims (10)

A method for preparing a smooth protective coating, which is formed on a substrate to be protected, the preparation method comprising: providing a low surface energy material; providing a surfactant; Carrying out a step of preparing a particle dispersion, which is to uniformly mix the low surface energy material and the surfactant to form a particle dispersion, and the particle dispersion contains a plurality of particles formed by the low surface energy material; performing a microparticle dispersion coating step, which is coating the microparticle dispersion on the substrate, and heat-treating the substrate coated with the microparticle dispersion to form an adhesive layer and a hole layer on the substrate, the hole layer is formed by the particles, the adhesive layer is formed by the surfactant and is located between the hole layer and the substrate; and Carrying out a lubricant coating step, which is to apply a lubricant to the hole layer, and wait for the lubricant to penetrate into the hole structure of the hole layer to form a smooth protective coating on the substrate; Wherein, the smooth protective coating includes the hole layer, the adhesive layer and the lubricant. The method for preparing a smooth protective coating as claimed in claim 1, wherein the low surface energy material is polytetrafluoroethylene or polydimethylsiloxane. The method for preparing a smooth protective coating as claimed in claim 2, wherein when the low surface energy material is polytetrafluoroethylene, the diameter of each of the particles in the particle dispersion is 100 nm to 300 nm. The method for preparing a smooth protective coating as claimed in claim 2, wherein when the low surface energy material is polydimethylsiloxane, the diameter of each of the particles in the particle dispersion is 10 μm to 40 μm. The method for preparing a smooth protective coating as claimed in item 1, wherein the surfactant is polyethylene glycol trimethyl nonyl ether. The method for preparing a smooth protective coating as claimed in claim 1, wherein the volume percentage concentration of the particles in the particle dispersion is 10% to 60%. The method for preparing a lubricating protective coating as described in Claim 1, wherein the lubricant is an ionic liquid, silicone oil or fluorine lubricating oil. The method for preparing a smooth protective coating as claimed in claim 1, wherein in the particle dispersion coating step, the substrate coated with the particle dispersion is heat-treated at a temperature of 100°C to 150°C for 5 minutes to 15 minutes. The method for preparing a smooth protective coating as claimed in claim 1, wherein the thickness of the smooth protective coating is 300 nm to 500 nm. A material with a smooth protective coating comprising: a substrate having a surface; and A smooth protective coating is formed on the surface of the substrate, and the smooth protective coating is prepared by the method for preparing a smooth protective coating as described in any one of claim 1 to claim 9.